Insecticidal and acaricidal composition and method with triazolyl phosphoric esters acid

ABSTRACT

Insecticidal and acaricidal composition and method utilizing triazolyl phosphoric acid esters of the formula ##EQU1##wherein R 1  represents a phenyl group susbstituted by one or more fluorine atoms or lower haloalkyl groups or by at least one chlorine atom and at least one fluorine atom or lower haloalkyl groups, R 2  and R 3  are each lower alkyl and X and Y are each oxygen or sulphur.

This is a divisional of application Ser. No. 302,691, filed on Nov. 1,1972, now U.S Pat. No. 3,875,179.

The present invention relates to new triazolyl phosphoric acid esters,their manufacture and their use in pest control.

According to the present invention there are provided triazolylphosphoric acid esters corresponding to the formula ##EQU2## wherein R₁represents a phenyl group substituted by one or more fluorine atoms orlower haloalkyl groups or by at least one chlorine atom and at least onefluorine atom or lower haloalkyl groups, R₂ and R₃ are each lower alkyland X and Y are each oxygen or sulphur.

Preferred lower haloalkyl groups are trifluoromethyl anddifluorochloromethyl.

Preferred on account of their activity are compounds of formula Iwherein R₁ is 4-fluorophenyl, 2,3,4,5,6-pentafluorophenyl,3-chloro-4-fluorophenyl, 2-trifluoromethylphenyl,3-trifluoromethylphenyl, 4-trifluoromethylphenyl,3-difluorochloromethylphenyl, 3-chloro-4-trifluoromethylphenyl,2-chloro-5-trifluoromethylphenyl, 3-trifluoromethyl-4-chlorophenyl, R₂is methyl or ethyl, R₃ is methyl, ethyl or propyl, and X and Y are eachoxygen or sulphur.

The compounds of formula I may be manufactured by reacting (a) ahydroxytriazole of the formula ##EQU3## with a phosphoric acid halide ofthe formula ##EQU4## in the presence of an acid binding agent, or (b) asalt of a hydroxytriazole of formula II with a phosphoric acid halide offormula III.

In formulae II and III the symbols R₁ to R₃ and X have the meaningsgiven for formula I and Hal stands for fluorine, chlorine, bromine oriodine, especially chlorine or bromine. Suitable salts ofhydroxytriazoles of formula II for use in the process according to theinvention are for example those of monovalent metals, particularly thealkali metal salts, but others may also be used, for example salts ofmonovalent heavy metals.

The following bases may be used, for example, as acid binding agents:tertiary amines such as triethylamine, dimethyl aniline, pyridine bases,inorganic bases, such as hydroxides and carbonates of alkali andalkaline earth metals, preferably sodium and potassium carbonate.

The reactions are preferably carried out in a solvent or diluent inertto the reactants. For this, the following are, for example, suitable:aromatic hydrocarbons such as benzene, toluene, petroleum ether,halohydrocarbons, chlorobenzene, polychlorobenzenes, bromobenzene,chlorinated alkanes with 1 to 3 carbon atoms, ethers such as dioxane,tetrahydrofuran; esters such as ethyl acetate; ketones such as methylethyl ketone, diethyl ketone, nitriles, etc.

The starting materials of formula II are partly known compounds whichcan be made by methods known per se. These compounds are obtained, forexample, by reacting a correspondingly substituted semicarbazide withorthocarboxylic acid ethyl esters, e.g. alkyl formates, or by firstformulating a correspondingly substituted semicarbazide followed by ringclosure under alkaline conditions.

In this way, the following novel starting materials of formula II may,for example, be made:

    ______________________________________                                        R.sub.1 --N------N                                                            |∥                                                          CHC--OH           Melting point                                               ∠                                                                       NR.sub.1                                                                      ______________________________________                                                        207 - 209                                                                     > 300                                                                         273 - 275                                                                     201 - 204                                                     ______________________________________                                                        +PG,7

The compounds of formula I have broad spectrum biocidal activity and canbe used for combating various vegetable and animal pests, for examplesas viricides, selective herbicides and molluscicides.

They are effective above all against all development stages such aseggs, larvae, nymphs, pupae and adults of insects and representatives ofthe order Acarina such as mites and ticks.

The compounds of formula I can be used for example against the followinginsects or representatives of the order Acarina: Insects of thefamilies: Teltigonidae, Gryllidae, Gryllotalpidae, Blattidae,Peduviidae, Phyrrhocoriae, Cimicidae, Delphacidae, Aphididae,Diaspididae, Pseudococcidae, Scarabaeidae, Dermestidae, Coccinellidae,Tenebrionidae, Chrysomelidae, Bruchidae, Tineidae, Noctuidae,Lymatriidae, Pyralidae, Culicidae, Tipulidae, Stomoxydae, Trypetidae,Muscidae, Calliphoridae and Pulicidae as well as Acarina of the familiesIxodidae, Argasidae, Tetranychidae and Dermanyssidae.

The insecticidal and/or acaricidal action can be substantially broadenedand matched to given circumstances by the addition of other insecticidesand/or acaricides.

As additives, the following active substances are, for example,suitable:

Organic phosphorus compounds

Bis- O,O-diethylphosphoric acid anhydride (TEPP)

Dimethyl-(2,2,2-trichloro-1-hydroxyethyl)-phosphonate (TRICHLORFON)

1,2-dibromo-2,2-dichloroethyldimethylphosphate (NALED)

2,2-dichlorovinyldimethylphosphate (DICHLORVOS)

2-methoxycarbamyl-1-methylvinyldimethylphosphate (MEVINPHOS)

Dimethyl-1-methyl-2-(methylcarbamoyl)-vinylphosphate cis (MONOCROTOPHOS)

3-(dimethoxyphosphinyloxy)-N,N-dimethyl-cis-crotonamide (DICROTOPHOS)

2-chloro-2-diethylcarbamoyl-1-methylvinyldimethylphosphate(PHOSPHAMIDON)

o,o-diethyl-O(or S)- 2-(ethylthio)-ethylthiophosphate (DEMETON)

S-ethylthioethyl-O,O-dimethyl-dithiophosphate (THIOMETON)

O,o-diethyl-S-ethylmercaptomethyldithiophosphate (PHORATE)

o,o-diethyl-S-2-ethylthio)ethyldithiophosphate (DISULFOTON)

o,o-dimethyl-S-2-(ethylsulphinyl)ethylthiophosphate (OXYDEMETONMETHYL)

o,o-dimethyl-S-(1,2-dicarbethoxyethyldithiophosphate (MALATHION)

O,o,o,o-tetraethyl-S,S' -methylene-bis-dithiophosphate (ETHION)

O-ethyl-S,S-dipropyldithiophosphate

O,o-dimethyl-S-(N-methyl-N-formylcarbamoylmethyl)-dithiophosphate(FORMOTHION)

O,o-dimethyl-S-(N-methylcarbamoylmethyl)dithiophosphate (DIMETHOATE)

O,o-dimethyl-O-p-nitrophenylthiophosphate (PARATHION-METHYL)

O,o-diethyl-O-p-nitrophenylthiophosphate (PARATHION)

O-ethyl-O-p-nitrophenylphenylthiophosphate (EPN)

O,o-dimethyl-O-( 4-nitro-m-tolyl)thiophosphate (FENITROTHION)

O,o-dimethyl-O- 2,4-5-trichlorophenylthiophosphate (RONNEL)

O-ethyl- 0,2,4,5-trichlorophenylethylthiophosphate (TRICHLORONATE)

O,o-dimethyl-O- 2,5-dichloro-4-bromophenylthiophosphate (BROMOPHOS)

O,o-dimethyl-O-( 2,5-dichloro-4-jodphenyl)-thiophosphate (JODOFENPHOS)

4-tert. butyl-2-chlorophenyl-N-methyl-O-methylamidophosphate (CRUFOMATE)

O,o-dimethyl-O-( 3-methyl-4-methylmercaptophenyl)thiophosphate(FENTHION)

Isopropylamino-O-ethyl-O-(4-methylmercapto-3-methylphenyl)-phosphate

O,o-diethyl-O-p-(methylsulphinyl)phenyl-thiophosphate (FENSULFOTHION)

O-p-(dimethylsulphamido)phenyl-O,O-dimethylthiophosphate (FAMPHUR)

O,o,o',o'-tetramethyl-O,O'-thiodi-p-phenylenethiophosphate

O-ethyl-S-phenyl-ethyldithiophosphate

2-chloro-1-(2,4-dichlorophenyl)vinyl-diethylphosphate (CHLORFENVINPHOS)

1-chloro-1-(2,4,5-trichlorophenyl)vinyl-dimethylphosphate

O-[ 2-chloro-1-(2,5-dichlorophenyl)] vinyl-O,O-diethylthiophosphate

Phenylglyoxylonitriloxim-O,O-diethylthiophosphate (PHOXIM)

O,o-diethyl-0-( 3-chloro-4-methyl-2-oxo-2-H-1-benzopyran-7-yl)thiophosphate (COUMAPHOS)

2,3-p-dioxandithiol-S,S-bis(O,O-diethyldithiophosphate) (DIOXATHION)

5-[(6-chloro-2-oxo-3-benzoxazolinyl)methyl]O,O-diethyldithiophosphate(PHOSALONE)

2-(diethoxyphosphinylimino)-1,3-dithiolane

O,o-dimethyl-S-[0,0-dimethyl-S-[2-methoxy-1,3,4-thiadiazol-5-(4H)-onyl-(4)-methyl]dithiophosphate

O,o-dimethyl-S-phthalimidomethyl-dithiophosphate (IMIDAN)

o,o-diethyl-O-(3,5,6-trichloro-2-pyridyl)thiophosphte

O,O,-diethyl-O-2-pyrazinylthiophosphate (THIONAZIN)

o,o-diethyl-O(2-isopropyl-4-methyl-6-pyrimidyl)thiophosphate (DIAZINON)

o,o-diethyl-O-(

o,o-dimethyl-O-(4-oxo-1,2,3-benzotriazine-3(4H)-ylmethyl)-dithiophosphate(AZINPHOSMETHYL)

o,o-diethyl-S-(4-oxo-1,2,3-benzotriazine-3(4H)-ylmethyl)-dithiophosphate(AZINPHOSETHYOL)

S-[(4,6-diamino-s-triazine-2-yl)methyl] O,O-dimethyldithiophosphate(MENAZON)

o,o-dimethyl-O-(3-chloro-4-nitrophenyl)thiophosphate (CHLORTHION)

o,o-dimethyl-O(or S)-2-(ethylthioethyl)thiophosphate (DEMETON-S-METHYL)o,o-dimethyl-phosphoryl-thiomethyl)-5-methoxy-pyron-4,3,4-dichlorobenzyl-triphenylphosphoniumchloride

O,O-diethyl-S-(2,5-dichlorophenylthiomethyl)dithiophosphate (PHENKAPTON)

o,o-diethyl-O-(4-methyl-cumarinyl-7-)-thiophosphate (POTASAN)

5-amino-bis(dimethylamido)phosphinyl-3-phenyl-1,2,4-triazole(TRIAMIPHOS)

N-methyl-5 -(O,O-dimethylthiolphosphoryl)-3-thiavaleramide (VAMIDOTHION)

o,o-diethyl-O-[ 2-diemthylamino-4-methylpyrimidyl-(6)]-thiophosphate(DIOCTHYL)

o,o-dimethyl-S-(methylcarbamoylmethyl)-thiophosphate (OMETHOATE)

O-ethyl-O-(8-quinolinyl)-phenylthiophosphonate (OXINOTHIOPHOS)

O-methyl-S-methyl-amidothiophosphate (MONITOR)

O-methyl-O-(2,5-dichloro-4-bromophenyl)-benzothiophosphate (PHOSVEL)

O,o,o,o-tetrapropyldithiophosphate

3-(dimethoxyphosphinyloxy)-N-methyl-N-methoxy-cis-crotonamide

O,o-diemthyl-S-(N-ethylcarbamoylmethyl)dithiophosphate (ETHOATE-METHYL)

O,o-diethyl-S-(N-isopropylcarbamoylmethyl)-dithiophosphate (PROTHOATE)

S-n-(1-cyano-1-methylethyl)carbamoylmethyldiethylthiolphosphate(CYANTHOATE)

S-(2-acetamidoethyl)-O,O-dimethyldithiophosphate

Hexamethylphosphoric acid triamide (HEMPA)

O,o-dimethyl-O-(2-chloro-4-nitrophenyl)thiophosphate (DICAPTHON)

O,o-dimethyl-O-p-cyanophenyl thiophosphate (CYANOX)

O-ethyl-O-p-cyanophenylthiophosphonate

O,o-diethyl-O-2,4-dichlorophenylthiophosphate (DICHLORFENTHION)

o,2,4-dichlorophenyl-O-methylisopropylamidothiophosphate

O,o-diethyl-O-2,5-dichloro-4-bromophenylthiophosphate (BROMOPHOS-ETHYL)

Dimethyl-p-(methylthio)phenylphosphate

O,o-dimethyl-O-p-sulfamidophenylthiophosphate

O-[p-(p-chlorophenyl)azophenyl]O,O-dimethylthiophosphate (AZOTHOATE)

O-ethyl-S-4-chlorophenyl-ethyldithiophosphate

O-isobutyl-S-p-chlorophenyl-ethyldithiophosphate

O,o-dimethyl-S-p-chlorophenylthiophosphate

O,o-dimethyl-S-(p-chlorophenylthiomethyl)dithiophosphate

O,o-diethyl-p-chlorophenylmercaptomethyl-dithiophosphate(CARBOPHENOTHION)

O,o-diethyl-S-p-chlorophenylthiomethyl-thiophosphate

O,o-dimethyl-S-(carbethoxy-phenylmethyl)dithiophosphate (PHENTHOATE)

O,o-diethyl-S-(carbofluorethoxy-phenylmethyl)-dithiophosphate

O,o-dimethyl-S-carboisopropoxy-phenylmethyl)-dithiophosphate

O,o-diethyl-7-hydroxy-3,4-tetramethylene-coumarinyl-thiophosphate(COUMITHOATE)

2-methoxy-4-H-1,3,2-benzodioxaphosphorin-2-sulphide

O,o-diethyl-O-(5-phenyl-3-isooxazolyl)thiophosphate

2-(diethoxyphosphinylimino)-4-methyl-1,3-dithiolane

Tris-(2-methyl-1-aziridinyl)-phosphine oxide (METEPA)

S-(2-chloro-1-phthalimidoethyl)-O,O-diethyldithiophosphate

N-hydroxynaphthalimido-diethylphosphate

Dimethyl-3,5,6-trichloro-2-pyridylphosphate

O,o-dimethyl-O-(3,5,6-trichloro-2-pyridyl)thiophosphate

S-2-(ethylsulphonyl)ethyl dimethylthiolphosphate (DIOXYDEMETON-S-METHYL)

Diethyl-S-2-(ethylsulphinyl)ethyl dithiophosphate (OXIDISULFOTON)

Bis-O,O-diethylthiophosphoric acid anhydride (SULFOTEP)

Dimethyl-1,3-di(carbomethoxy)-1-propen-2-yl-phosphate

Dimethyl-(2,2,2-trichloro-1-butyroyloxyethyl)phosphonate (BUTONATE)

O,o-dimethyl-O-(2,2-dichloro-1-methoxy-vinyl)phosphate

Bis-(dimethylamido)fluorphosphate (DIMEFOX)

3,4-dichlorobenzyl-triphenylphosphoniumchloride

Dimethyl-N-methoxymethylcarbamoylmethyl-dithiophosphate (FORMOCARBAM)

O,o-diethyl-O-(2,2-dichloro-1-chloroethoxyvinyl)phosphate

O,o-dimethyl-O-(2,2-dichloro-1-chloroethoxyvinyl)phosphate

O-ethyl-S,S-diphenyldithiolphosphate

O-ethyl-S-benzyl-phenyldithiophosphonate

O,o-diethyl-S-benzyl-thiolphosphate

O,o-dimethyl-S-(4-chlorophenylthiomethyl)dithiophosphate(METHYLCARBOPHENOTHION)

O,o-dimethyl-S-(ethylthiomethyl)dithiophosphate

Diisopropylaminofluorophosphate (MIPAFOX)

O,o-dimethyl-S-(morpholinylcarbamoylmethyl)dithiophosphate (MORPHOTHION)

Bismethylamido-phenylphosphate

O,o-dimethyl-S-(benzene sulphonyl)dithiophosphate

O,o-dimethyl-(S and O)-ethylsulphinylethylthiophosphate

O,o-diethyl-O-4-nitrophenylphosphate

Triethoxy-isopropoxy-bis(thiophosphinyl)disulphide

2-methoxy-4H-1,3,2,benzodioxaphosphorin-2-oxide

Octamethylpyrophosphoramide (SCHRADAN)

Bis (dimethoxythiophospphinylsulphido)-phenylmethane

N,n,n',n'-tetramethyldiamidofluorophosphate (DIMEFOX)

O-phenyl-O-p-nitrophenyl-methanthiophosphonate (COLEP)

O-methyl-O-(2-chloro-4-tert.butyl-phenyl)-N-methylamidothiophosphate(NARLENE)

O-ethyl-O-(2,4-dichlorophenyl)-phenylthiophosphonate

O,o-diethyl-O-(4-methylmercapto-3,5-dimethylphenyl)-thiophosphate

4,4'-bis-(O,O-dimethylthiophosphoryloxy)-diphenyl disulphide

O,o-di-(β-chloroethyl)-O-(3-chloro-4-methyl-coumarinyl-7)-phosphate

S-(1-phthalimidoethyl)-O,O-diethyldithiophosphate

O,o-dimethyl-O-(3-chloro-4-diethylsulphamylphenyl)-thiophosphate

O-methyl-O-(2-carbisopropoxyphenyl)-amidothiophosphate

5-(O,O-dimethylphosphoryl)-6-chloro-bicyclo(3.2.0)-heptadiene (1,5)

O-methyl-O-(2-i-propoxycarbonyl-1-methylvinyl)-ethylamidothiophosphate.

Ritrophenols and derivatives

4,6-dinitro-6-methylphenol, Na-salt [Dinitrocresol]

dinitrobutylphenol-(2,2',2"-triethanolamine salt

2-cyclohexyl-4,6-dinitrophenyl [Dinex]

2-(1-methylheptyl)-4,6-dinitrophenyl-crotonate [Dinocap]

2-sec.-butyl-4,6-dinitrophenyl-3-methyl-butenoate [Binapacryl]

2-sec.-butyl-4,6-dinitrophenyl-cyclopropionate

2-sec.-butyl-4,6-dinitrophenylisopropylcarbonate [Dinobuton]

Miscellaneous

pyrethin I

pyrethin II

3-allyl-2-methyl-4-oxo-2-cyclopentan-1-yl-chrysanthemumate (Allethrin)

6-chloriperonyl-chrysanthemumate (Barthrin)

2,4-dimethylbenzyl-chrysanthemumate (Dimethrin)

2,3,4,5-tetrahydrophthalimidomethylchrysanthemumate

4-chlorobenzyl-4-chlorophenylsulphide [Chlorobensid]

6-methyl-2-oxol, 3-dithiolo-[4,5-b]-quinoxaline [Quinomethionate]

(I)-3-(2-furfuryl)-2-methyl-4-oxocyclopent-2-enyl(I)-(cis+trans)-chrysanthemum-monocarboxylate[Furethrin]

2-pivaloyl-indane-1,3-dione [Pindon]

N'-(4-chloro-2-methylphenyl)-N,N-dimethylformamidine [Chlorophenamidin]

4-chlorobenzyl-4-fluorophenyl-sulphide [Fluorobenside]

5,6-dichloro-1-phenoxycarbanyl-2-trifluoromethyl-benzimidazole[Fenozaflor]

p-chlorophenyl-p-chlorobenzenesulphonate [Ovex]

p-chlorophenyl-benzenesulphonate [Fenson]

p-chlorophenyl-2,4,5-trichlorophenylsulphone [Tetradifon]

p-chlorophenyl-2,4,5-trichlorophenylsulphide [Tetrasul]

p-chlorobenzyl-p-chlorophenylsulphide [Chlorobenside]

2-thio-1,3-dithiolo-(,5-6)-quinoxaline [Thiochinox]

prop-2-ynyl-(4-t-butylphenoxy)-cyclohexylsulphite [Propargil].

Formamidines

1-dimethyl-2-(2'-methyl-4'-chlorophenyl)-formamidine (CHLORPHENAMIDIN)

1-methyl-2-(2'-methyl-4'-chlorophenyl)-formamidine

1-methyl-2-(2'-methyl-4'-bromophenyl)-formamidine

1-methyl-2-(2',4'-dimethylphenyl)-formamidine

1-n-butyl-1-methyl-2-(2'-methyl-4'-chlorophenyl)-formamidine

1-methyl-1-(2'-methyl-4'-chloroaniline-methylene)-formamidine

2-(2"-methyl-4"-chlorophenyl)-formamidine

1-n-butyl-2-(2'-methyl-4'-chlorophenyl-imino)-pyrolidine.

Urea

N-2-methyl-4-chlorophenyl-N',N'-dimethyl-thiourea.

Carbamate

1-naphthyl-N-methylcarbamate (CARBARYL)

2-butinyl-4-chlorophenylcarbamate

4-dimethylamino-3,5-xylyl-N-methylcarbamate

4-dimethylamino-3-tolyl-N-methylcarbamate (AMINOCARB)

4-methylthio-3,5-xylyl-N-methylcarbamate (METHIOCARB)

3,4,5-trimethylphenyl-N-methylcarbamate

2-chlorophenyl-N-methylcarbamate (CPMC)

5-chloro-6-oxo-2-norborane-carbonitrile-O-)methylcarbamoyl)-oxime

1-(dimethylcarbamoyl)-5-methyl-3-pyrazolyl-N,N-dimethylcarbamate(DIMETILAN)

2,3-dihydro-2,2-dimethyl-7-benzofuranyl-N-methylcarbamate (CARBOFURAN)

2-methyl-2-methylthio-propionaldehyde-O-(methylcarbamoyl)-oxime(ALDECARB)

8-chinaldyl-N-methylcarbamate and their salts

methyl 2-isopropyl-4-(methylcarbamoyloxy)carbanilate

m-(1-ethylpropyl)phenyl-N-methylcarbamate

3,5-di-tert.butyl-N-methylcarbamate

m-(1-methylbutyl)phenyl-N-methylcarbamate

2-isopropylphenyl-N-methylcarbamate

2-sec.butylphenyl-N-methylcarbamate

m-tolyl-N-methylcarbamate

2,3-xylyl-N-methylcarbamate

3-isopropylphenyl-N-methylcarbamate

3-tert.butylphenyl-N-methylcarbamate

3-sec.butylphenyl-N-methylcarbamate

3-isopropyl-5-methylphenyl-N-methylcarbamate (PROMECARB)

3,5-diisopropylphenyl-N-methylcarbamate

2-chloro-5-isopropylphenyl-N-methylcarbamate

2-chloro-4,5-dimethylphenyl-N-methylcarbamate

2-(1,3-dioxolan-2-yl)phenyl-N-methylcarbamate (DIOXACARB)

2-(4,5-dimethyl-1,3-dioxolan-2-yl)phenyl-N-methylcarbamate

2-(1,3-dioxolan-2-yl)phenyl-N,N-dimethylcarbamate

2-(1,3-dithiolan-2-yl)-N,N-dimethylcarbamate

2-(1,3-dithiolan-2-yl)phenyl-N,N-dimethylcarbamate

2-isopropoxyphenyl-N-methylcarbamate (APROCARB)

2-(2-propinyloxy)phenyl-N-methylcarbamate

3-(2-propinyloxy)phenyl-N-methylcarbamate

2-dimethylaminophenyl-N-methylcarbamate

2-diallylaminophenyl-N-methylcarbamate

4-diallylamino-3,5-xylyl-N-methylcarbamate (ALLYXICARB)

4-benzothienyl-N-methylcarbamate

2,3-dihydro-2-methyl-7-benzofuranyl-N-methylcarbamate

3-methyl-1-phenylpyrazol-5-yl-N,N-dimethylcarbamate

1-isopropyl-3-methylprazol-5-yl-N,N-dimethylcarbamate (ISOLAN)

2-dimethylamino-5,6-dimethylpyrimidin-4-yl-N,N-dimethyl-carbamate

3-methyl-4-dimethylaminomethyleneiminophenyl-N-methylcarbamate

3-dimethylamino-methyleneiminophenyl-N-methylcarbamate (FORMETANATE) andtheir salts

1-methylthio-ethylimino-N-methylcarbamate (METHOMYL)

2-methylcarbamoyloximino-1,3-dithiolane

5-methyl-2-methylcarbamoyloximino-1,3-oxythiolane

2-(1-methoxy-2-propoxy)phenyl-N-methylcarbamate

2-(1-butin-3-yl-oxy)phenyl-N-methylcarbamate

1-dimethylcarbamyl-1-methylthio-O-methylcarbamyl-formoxime

1-(2'-cyanoethylthio)-O-methylcarbamyl-acetaldoxime

1-methylthio-O-carbamyl-acetaldoxime

O-(3-sec.butylphenyl)-N-phenylthio-N-methylcarbamate

2,5-dimethyl-1,3-dithioland-2-(O-methylcarbamyl)-aldoxime)

O-2-diphenyl-N-methylcarbamate

2-(N-methylcarbamyl-oximino)-3-chloro-bicyclo[2.2.1]heptane

2-(N-methylcarbamyl-oximino)-bicyclo[2.2.1]heptane

3-isopropylphenyl-N-methyl-N-chloroacetyl-carbamate

3-isopropylphenyl-N-methyl-N-methylthiomethyl-carbamate

O-(2,2-dimethyl-4-chloro-2,3-dihydro-7-benzofuranyl)-N-methylcarbamate

O-(2,2,4-trimethyl-2,3-dihydro-7-benzofuranyl)-N-methylcarbamate

O-naphthyl-N-methyl-N-acetyl-carbamate

O-5,6,7,8-tetrahydronaphthyl-N-methyl-carbamate

3-isopropyl-4-methylthio-phenyl-N-methylcarbamate

3,5-dimethyl-4-methoxy-phenyl-N-methylcarbamate

3-methoxymethoxy-phenyl-N-methylcarbamate

3-allyloxyphenyl-N-methylcarbamate

2-propargyloxymethoxy-phenyl-N-methyl-carbamate

2-allyloxyphenyl-N-methyl-carbamate

4-methoxycarbonylamino-3-isopropylphenyl-N-methyl-carbamate

3,5-dimethyl-4-methoxycarbonylamino-phenyl-N-methyl-carbamate

2-γ-methylthiopropylphenyl-N-methyl-carbamate

3-(α-methoxymethyl-2-propenyl)-phenyl-N-methyl-carbamate

2-chloro-5-tert.-butyl-phenyl-N-methyl-carbamate

4-(methyl-propargylamino)-3,5-xylyl-N-methyl-carbamate

4-(methyl-γ-chloroallylamino)-3,5-xylyl-N-methyl-carbamate

4-(methyl-β-chloroallylamino)-3,5-xylyl-N-methyl-carbamate

1-(β-ethoxycarbonalethyl)-3-methyl-5-pyrazolyl-N,N-dimethylcarbamate

3-methyl-4(dimethylamino-methylmercapto-methylencimino)phenyl-N-methylcarbamate

1,3-bis(carbamoylthio)-2-(N,N-dimethylamino)-propanehydrochloride

5,5-dimethylhydroresorcinoldimethylcarbamate

2-[ethyl-propargylamino]-phenyl-N-methylcarbamate

2-[methyl-propargylamino]-phenyl-N-methylcarbamate

2-[dipropargylamino]-phenyl-N-methylcarbamate

4-[dipropargylamino]-3-tolyl-N-methylcarbamate

4-[dipropargylamino]-3,5-xylyl-N-methylcarbamate

2-[allyl-isopropylamino]-phenyl-N-methylcarbamate

3-[allyl-isopropylamino]-phenyl-N-methylcarbamate

Chlorinated Hydrocarbons

γ-hexachlorocyclohexane [GAMMEXANE; LINDAN; γ HCH]

1,2,4,5,6,7,8,8-octachloro-3α,4,7,7α'tetrahydro-4,7-methylenindane[CHLORDAN]

1,4,5,6,7,8,8-heptachloro,3α,4,7,7α-tetrahydro-4,7-methylenindane[HEPTACHLOR]

1,2,3,4,10,10-hexachloro-1,4,4α,5,8,8α-hexahydro-endo-1,4-exo-5,8-dimethanonaphthalene[ALDRIN]

1,2,3,4,10,10-hexachloro-6,7-epoxy-1,4,4α,5,6,7,8,8α-oxtahydro-exo-1,4-endo-5,8-dimethanonaphthalene(DIELDRIN)

1,2,3,4,10,10-hexachloro-5,7-epoxy-1,4,4α,5,6,7,8,8α-octyhydro-endo-endo-5,8-dimethanonaphthalene [ENDRIN]

The active substances of formula I are suitable for combatingrepresentatives of the order Thallophyta, such as bacteria and fungi.Especially they possess fungicidal properties against phytopathogenicfungi of the following classes: Oomycetes, Phycomycetes, Ascomycetes,Basidiomycetes, Denteromycetes.

Because of their biocidal properties, the compounds of formula I can beused not only in plant protection but also for disinfecting andprotecting various types of material from fungal attack. In thisconnection, it has proved particularly advantageous that the compoundsof formula I generate no poisonous effects in warmblooded animals in theconcentrations necessary for disinfection and materials protection.

The compounds of formula I can be formulated in various mixing ratioswith known fungicides and microbicides, whereby mixtures of compoundsarise with advantages compared to the individual components. Thefollowing known fungicides are, for example, suitable for formulatingwith the active substances of formula I:

dodecylguanidine acetate (DODINE)

pentachloronitrobenzene (QUINTOZENE)

pentachlorophenol (PCP)

2-(1-methyl-n-propyl)-4,6-dinitrophenyl-2-methyl-crotonate (BINAPACRYL)

2-(1-methyl-n-heptyl)-4,6-dinitrophenylcrotonate (DINOCAP)

2,6-dichloro-4-nitroaniline (DICHLORAN)

2,3,5,6-tetrachloro-benzoquinone (1,4) (CHLORANIL)

2,3-dichloro-naphthoquinone (1,4) (DICHLONE)

N-(trichloromethylthio) phthalimide (FOLPAT)

N-(trichloromethylthio) cyclohex-4-en-1,2-dicarboximide (CAPTAN)

N-(1,1,2,2-tetrachloroethylthio)cyclohex-4-en-1,2-dicarboximide(CAPTAFOL)

N-methansulfonal-N-trichloromethylthio-chloroaniline

N'-dichlorofluoromethylthio-N,N-dimethyl-N'-phenylsulfamide(DICHLOFLUANID)

O-ethyl-S-benzyl-phenyldithiophosphate

O,o-diethyl-S-benzyl-thiolphosphate

disodium-ethylene-1,2-bis-dithiocarbamate (NABAM)

zinc-ethylene-1,2-bis-dithiocarbamate (ZINEB)

manganese-ethylene-1,2-bis-dithiocarbamate (polymeric) (MANEB)

tetramethylthiuramdisulfide (THIRAM)

1-oxy-3-acetyl-6-methyl-cyclohexene-(5)dione-(2,4) (DEHYDROACETIC ACID)

8-hydroxyquinoline (8-QUINOLINOL)

2-dimethylamino-6-methyl-5-n-butyl-4-hydroxy-pyrimidine

methyl-N-benzimidazole-2-yl-N-(butylcarbamoyl)carbamate (BENOMYL)

2-ethylamino-6-methyl-5n-butyl-4-hydroxypyrimidine

2,3-dicyano-1,4-dithia-anthraquinone (DITHIANON)

2-(4-thiazolyl)-benzimidazole

3,5-dimethyltetrahydro-1,3,5-thiadiazin-2-thione (DAZOMET)

2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathine

pentachlorobenzyl alcohol.

Additionally, the new compounds of formula I possess nematocidalproperties, and can be used, for example, to combat the following plantparasitic nematodes: Meloidogyne sp., Heterodera sp., Ditylenchus sp.,Pratylenchus sp., Paratylenchus sp., Anguina sp., Helicotylenchus sp.,Tylenchorhynchus sp., Rotylenchulus sp., Tylenchulus semipenetrans,Radopholus similus, Belonolaimus sp., Trichodorus sp., Longidorus sp.,Aphelenchoides sp., Xiphinema sp.

The compounds of the formula I may be used as pure active substance ortogether with suitable carriers and/or additives. Suitable carriers andadditives can be solid or liquid and correspond to the substancesconventionally used in formulation technique such, for example, assolvents dispersants, wetting agents, adhesives, thickeners, bindersand/or fertilisers.

For application, the compounds of the formula I may be processed todusts, emulsion concentrates, granules, dispersions, sprays, tosolutions, or suspensions in the conventional formulation which iscommonly employed in application terminology. Mention may also be madeof "cattle dips" and "spray races", in which aqueous preparations areused.

The agents according to the invention are manufactured in known mannerby intimately mixing and/or grinding active substances of the formula Iwith the suitable carriers, optionally with the addition of dispersantsor solvents which are inert towards the active substances. The activesubstances may be available and can be used in the following forms:

Solid forms

Dusts, tracking agents, granules, coated granules, impregnated granulesand homogeneous granules.

Liquid forms:

a. active substance concentrates dispersible in water: wettable powders,pastes, emulsions;

b. solutions.

To manufacture solid forms (dusts, tracking agents), the activesubstances are mixed with solid carriers. Suitable carriers are, forexample: kaolin, talcum, bolus, loess, chalk, limestone, groundlimestone, attaclay, dolomite, diatomaccous earth, precipitated silica,alkaline earth silicates, sodium and potassium aluminum silicates(feldspar and mica), calcium and magnesium sulphates, magnesium oxide,ground synthetic materials, fertilisers, for example ammonium sulphate,ammonium phosphate, ammonium nitrate, urea, ground vegetable products,such as corn meal, bark dust, sawdust, nutshell meal, cellulose powder,residues of plant extractions, activated charcoal etc. These substancescan either be used alone or in admixture with one another.

Granules can be very easily manufactured by dissolving an activesubstance of the formula I in an organic solvent and applying theresulting solution to a granulated material, for example attapulgite,SiO₂, granicalcium, bentonite etc. and then evaporating the solvent.

Polymer granules can also be manufactured by mixing the activesubstances of the formula I with polymerisable compounds(urea/formaldehyde; dicyandiamide/formaldehyde; melamine/formaldehyde orothers), whereupon a mild polymerisation is carried out that does notaffect the active substances and in the process of which the granulationis carried out during the gel formation. It is more advantageous toimpregnate finished, porous polymer granules (urea/formaldehyde,polyacrylonitrile, polyester or others) which have a specific surfacearea and a favourable predeterminable adsorption/desorption ratio, withthe active substances, for example in the form of their solutions (in alow boiling solvent) and to remove the solvent. Polymer granules of thiskind in the form of microgranules having a bulk density of 300 g/literto 600 g/liter can also be manufactured with the aid of atomisers. Thedusting can be carried out from aircraft over extensive areas ofcultures of useful plants.

It is also possible to obtain granules by compacting the carrier withthe active substance and carriers and subsequently comminuting theproduct.

To these mixtures can also be added additives which stabilize the activesubstance and/or non-ionic, anionic and cationic surface activesubstances, which for example improve the adhesion of the activeingredients on plants or parts of plants (adhesives and agglutinants)and/or ensure a better wettability (wetting agents) and dispersibility(dispersing agents). Examples of suitable adhesives and the following:olein/chalk mixture, cellulose derivatives (methyl cellulose,carboxymethyl cellulose), hydroxyethyl glycol ethers of monoalkyl anddialkyl phenols having 5 to 15 ethylene oxide radicals per molecule and8 to 9 carbon atoms in the alkyl radical, lignin sulfonic acids, theiralkali metal and alkaline earth metal salts, polyethylene glycol ethers(carbowaxes), fatty alcohol polyethylene glycol ethers having 5 to 20ethylene oxide radicals per molecule and 8 to 18 carbon atoms in thefatty alcohol moiety, condensation products of ethylene oxide/propyleneoxide, polyvinyl pyrrolidones, polyvinyl alcohols, condensation productsof urea and formaldehyde, and also latex products.

The water-dispersible concentrates of the active substance, i.e.wettable powders, pastes and emulsifiable concentrates, are agents whichcan be diluted with water to any concentration desired. They consist ofactive substance, carrier, optionally additives which stabilize theactive substance, surface-active substance and anti-foam agents and,optionally, solvents.

Wettable powders and pastes are obtained by mixing and grinding theactive substances with dispersing agents and pulverulent carriers insuitable apparatus until homogeneity is attained. Carriers are, forexample, those mentioned for the solid forms of application. In somecases it is advantageous to use mixtures of different carriers. Asdispersing agents there can be used, for example, condensation productsof sulfonated naphthalene and sulfonated naphthalene derivatives withformaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol and formaldehyde, as well as alkali, ammoniumand alkaline earth metal salts of lignin sulfonic acid, in addition,alkylaryl sulfonates, alkali and alkaline earth metal salts of dibutylnaphthalene acid, fatty alcohol sulfates such as salts of sulfatedhexadecanols, heptadecanols, octadecanols, and salts of sulfated fattyalcohol glycol ethers, the sodium salt of oleyl methyl tauride,ditertiary ethylene glycols, dialkyl dilauryl ammonium chloride andfatty acid alkali and alkaline earth metal salts.

Suitable anti-foam agents are silicone oils.

The active substances are mixed, ground, sieved and strained with theadditives mentioned above that, in wettable powder, the solid particlesize of from 0.02 to 0.04 and in pasts, of 0.03 mm is not exceeded. Toproduce emulsifiable concentrates and pastes, dispersing agents such asthose cited above, organic solvents and water are used. Examples ofsuitable solvents are the following: alcohols, benzene, xylenes,toluene, dimethyl sulfoxide, and mineral oil fractions boiling between120° and 350° C. The solvents must be practically odourless notphytotoxic, inert to the active substances.

Furthermore, the agents according to the invention can be applied in theform of solutions. For this purpose the active substance or severalactive substances of the general formula I are dissolved in suitableorganic solvents, mixtures of solvents or in water. Aliphatic andaromatic hydrocarbons, chlorinated derivatives thereof, alkylnaphthalenes, and mineral oils alone or mixed with each other, can beused as organic solvents.

The content of active substance in the above described agents is between0.1% to 95%, in which connection it should be mentioned that in the caseof application from aircraft or some other suitable means ofapplication, it is possible to use concentrations of up to 99.5% or evenpure active substance.

The active substances of the formula I can, for example, be formulatedas follows:

Dusts

The following substances are used to manufacture (a) a 5% and (b) a 2%dust:

a.

5 parts of active substance

95 parts of talcum

b.

2 parts of active substance

1 part of highly disperse silica

97 parts of talcum.

The active substances are mixed with the carriers and ground.

Granules

The following substances are used to produce 5% granules:

5 parts of active substance

0.25 parts of epichlorohydrin

0.25 parts of cetyl polyglycol ether

3.50 parts of polyethylene glycol

91 parts of kaolin (particle size 0.3-0.8 mm).

The active substance is mixed with epichlorohydrin and dissolved with 6parts of acetone; the polyethylene glycol and cetyl polyglycol ether arethen added. The thus obtained solution is sprayed on to kaolin, and theacetone subsequently evaporated in vacuo.

Wettable powder

The following constituents are used for the preparation of (a) a 40%,(b) and (c) a 25%, and (d) a 10% wettable powder:

a.

40 parts of active substance

5 parts of sodium lignin sulphonate

1 part of sodium dibutyl-naphthalene sulphonate

54 parts of silica acid.

b.

25 parts of active substance

4.5 parts of calcium lignin sulphonate

1.9 parts of Champagne chalk/hydroxyethyl cellulose mixture (1:1)

1.5 parts of sodium dibutyl naphthalene sulphate

19.5 parts of silica acid

19.5 parts of Champagne chalk

28.1 parts of kaolin.

c.

25 parts of active substance

2.5 parts of isooctylphenoxy-polyoxyethylene-ethanol

1.7 parts of Champagne chalk/hydroxyethyl cellulose mixture (1:1)

8.3 parts of sodium aluminium silicate

16.5 parts of kieselgur

46 parts of kaolin.

d.

10 parts of active substance

5 parts of naphthalenesulphonic acid/formaldehyde condensate

82 parts of kaolin.

The active substances are intimately mixed, in suitable mixers, with theadditives, the mixture being then ground in the appropriate mills androllers. Wettable powder are obtained which can be diluted with water togive suspensions of any desired concentration.

Emulsifiable concentrates

The following substances are used to produce (a) a 10% and (b) a 25%emulsifiable concentrate:

a.

10 parts of active substance

3.4 parts of epoxidised vegetable oil

13.4 parts of a combination emulsifier consisting of fatty alcoholpolyglycol ether and alkylarylsulphonate calcium salt

40 parts of dimethylformamide

43.2 parts of xylene.

b.

25 parts of active substance

2.5 parts of epoxidised vegetable oil

10 parts of an alkylarylsulphonate/fatty alcoholpolyglycol ether mixture

5 parts of dimethylformamide

57-5 parts of xylene.

From these concentrates it is possible to produce, by dilution withwater, emulsion of any desired concentration.

Spray

The following constituents are used to prepare a 5% spray:

5 parts of active substance

1 part of epichlorohydrin

94 parts of benzine (boiling limits 160°-190°C).

The following examples will serve to illustrate the preparation ofcompounds according to the invention and their properties:

EXAMPLE 1O,O-diethyl-O-[1-(3-trifluoromethylphenyl)-1,2,4-triazolyl-(3)]-thiophosphate

a. 23.9 g 1-(3-trifluoromethylphenyl)-semicarbazide and 14.8.gorthoformic acid ester were heated together with 40 ml glycol monomethylether whereon a clear yellow solution was obtained. The ethanol formingat an internal temperature of 120°C was continuously distilled off.After 41/2 hours the mixture was allowed to cool and treated with 200 mlether. The compound of the formula ##SPC1##

was obtained, having a decomposition point of 210°C.

b. 40 g 1-(3-trifluoromethylphenyl)-3-hydroxy-1,2,4-triazole and 23.6 gpotash were heated for 1 hour under reflux together with a spatula pointof copperbronze in 400 ml methyl ethyl ketone. Then 32.2 g O,O-diethylthiophosphoric acid chloride were added dropwise at 50°C. After threehours heating under reflux, the solvent was evaporated in vacuo. Theresidue was taken up in ether and washed successively with water, 0.5NHCl, saturated bicarbonate solution and brine. After drying over sodiumsulphate the ether was evaporated in vacuo to leave the crude product.By filtration through 800 g silica gel with methylene chloride assolvent, the compound of the formula ##SPC2##

is obtained. M.Pt.: 37°-39°C.

The following compounds were also made in analogous fashion:

           R.sub.1 --N------N                                                            |∥SOR.sub.2                                                 |∥∥                                                CHC--O--P∠                                                              ∠                                                                       NYR.sub. 3                                                             R.sub.1    R.sub.2 R.sub.3   Y                                                ______________________________________                                                 C.sub.2 H.sub.5                                                                     C.sub.2 H.sub.5                                                                         0     M.Pt.: 59-60°C                                   C.sub.2 H.sub.5                                                                     (n)C.sub.3 H.sub.7                                                                      S     n.sub.D.sup.20 = 1.5421                                 C.sub.2 H.sub.5                                                                     C.sub.2 H.sub.5                                                                         O     M.Pt.: 57-59°C                                   C.sub.2 H.sub.5                                                                     C.sub.2 H.sub.5                                                                         O     M.Pt.: 51-53°C                                   C.sub.2 H.sub.5                                                                     C.sub.2 H.sub.5                                                                         O     n.sub.D.sup.20 = 1.4926                                 C.sub.2 H.sub.5                                                                     (n)C.sub.3 H.sub.7                                                                      S                                                             C.sub.2 H.sub.5                                                                     C.sub.2 H.sub.5                                                                         O                                                             C.sub.2 H.sub.5                                                                     C.sub.2 H.sub.5                                                                         O                                                             C.sub.2 H.sub.5                                                                     C.sub.2 H.sub.5                                                                         O                                                             C.sub.2 H.sub.5                                                                     C.sub.2 H.sub.5                                                                         O                                                             CH.sub.3                                                                            CH.sub.3  O                                                             CH.sub.3                                                                            CH.sub.3  O                                                             C.sub.2 H.sub.5                                                                     (n)C.sub.3 H.sub.7                                                                      S                                                    ______________________________________                                    

EXAMPLE 2 Insecticidal ingest poison action

Cotton and potato plants are sprayed with a 0.05% aqueous emulsion(obtained from a 10% emulsifiable concentrate).

After the coating has dried, Disdercus fasciatus nymphs are settled onthe cotton plants and Colorado potato beetle larvae (Leptinotarsadecemlineata) on the potato plants. The test is carried out at 24°C and60% relative humidity. In the above test the compounds according toExample 1 displayed good ingest poison action against Disdercusfasciatus and Leptinotarsa decemlineata.

EXAMPLE 3 Acaricidal action

a. Action on mites (Tetranychus urticae)

For testing the acaricidal action bean leaves infested with adults, reststages and eggs of the red spidermite (Tetranychus urticae), weretreated with a 0.05% aqueous emulsion of the substance to be tested(made from a 25% emulsifiable concentrate). The test was evaluated after6 days. Phosphoric acid ester resistant strains of red spidermite wereused as test animals.

b. Action on ticks (Boophilus microplus) and their development stages

For the following test in each case 10 adult ovipositing ticks weredipped for three minutes in aqueous emulsions of active substance(Concentrations: 800; 400; 200; 100; 50; 10 and 1 ppm).

The ticks were then kept at 27°C and 80% relative humidity. Egglayingwas determined at the 5th, 10th and 15th day.

The compounds according to example 1 tested according to the above tests(a) and (b) showed good action against Tetranychus urticae and Boophilusmicroplus.

Action against soil nematodes

To test the action against soil nematodes, the active substance (in theconcentration indicated in each case is applied to and intimately mixedwith soil infected with root gall nematodes (Meloidgyne avenaria).Immediately afterwards, tomato cuttings are planted in the thus preparedsoil in a series of tests and after a waiting time of 8 days tomatoseeds are sown in another test series.

In order to assess the nematocidal action, the galls present on theroots are counted 28 days after planting and sowing respectively. Thecompounds according to Example I display good action against Meloidgyneavenaria is this test.

What we claim is:
 1. An insecticidal or acaricidal compositioncomprising an insecticidally or acaricidally effective amount of acompound of the formula ##EQU5##wherein R₁ represents phenyl substitutedby one to five fluorines or halo-lower alkyls, or by one chlorine andone substituent selected from the group consisting of fluorine andhalo-lower alkyl; R₂ and R₃ are each lower alkyl; and X and Y are eachoxygen or sulfur; together with a suitable carrier therefor.
 2. Thecomposition of claim 1, wherein R₁ is 4-fluorophenyl,2,3,4,5,6-pentafluorophenyl, 3-chloro-4-fluorophenyl,2-trifluoromethylphenyl, 3-trifluoromethylphenyl,4-trifluoromethylphenyl, 3-difluorochloromethylphenyl,3-chloro-4-trifluoromethylphenyl, 2-chloro-5-trifluoromethylphenyl or3-trifluoromethyl-4-chlorophenyl, R₂ is methyl or ethyl, R₃ is methyl,ethyl or propyl, and X and Y are each oxygen or sulphur.
 3. Thecomposition of claim 2, wherein said compound is ##SPC3##
 4. Thecomposition of claim 2, wherein said compound is ##SPC4##
 5. Thecomposition of claim 2, wherein said compound is ##SPC5##
 6. Thecomposition of claim 2, wherein said compound is ##SPC6##
 7. Thecomposition of claim 2, wherein said compound is ##SPC7##
 8. Thecomposition of claim 2, wherein said compound is ##SPC8##
 9. A methodfor combatting insects or acaride which comprises applying to the locusthereof an insecticidally or acaricidally effective amount of a compoundof the formula of claim
 1. 10. The method of claim 9, wherein R₁ is4-fluorophenyl, 2,3,4,5,6-pentafluorophenyl, 3-chloro-4-fluorophenyl,2-trifluoromethylphenyl, 3-trifluoromethylphenyl,4-trifluoromethylphenyl, 3-difluorochloromethylphenyl,3-chloro-4-trifluoromethylphenyl, 2-chloro-5-trifluoromethylphenyl or3-trifluoromethylphenyl-4-chlorophenyl, R₂ is methyl or ethyl, R₃ ismethyl, ethyl or propyl, and X and Y are each oxygen or sulphur.